Nondiffusing sulphonamide coupler for color photography



Patented Jan. 4, 1944 UNITED STATES PATENT 'OFFlCE I NONDI'FFUSINGSULPHONAMIDE COUPLER FOR COLOR PHOTOGRAPHY Arnold Weissberger,Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Original application August 22,1940, Serial No. 353,669, now Patent No.

2,298,443, dated October 13, 1942. Divided and this application May 1,1942, Serial No. 441,278. In Great Britain April 24, 1940 8 Claims. (Cl.95-6) 1940, now Patent No. 2,298,443, issued October Color formingcompounds which react with the development product of aromatic aminodeveloping agents to iform colored images on photographic development'have been the subject of numerous prior patents. The dyes formed in thisway are insoluble in water and in-the ordinary photographic developingand fixing baths, although the silver images formed simultaneously withthem during the photographic development may be removed from thephotographic layer to leave pure dye images in the layer. Such acompound which is employed in conjunction with the developing agent forthe silver and which couples with the development product of thedeveloper during photographic development is referred to herein as acoupling component or coupler. When these coupling components areincorporated in the photographic layer prior to exposure, they do notafiect the exposure and development of the layer in the usual way butwhen the development is carried out with a suitable developing agentthey combine with the oxidation product of the developer to form acolored image in situ with the silver image. a

In Vit um, Peterson and Porter U. S. application Serial No. 404,235,filed July 26, 1941, a. continuation-in-part of U. S. Patent No.2,271,238, ranted January 27, 1942, coupling components are describedwhich contain sulphonamide groups, Such couplers are desirable by reasonof their solubility characteristics and the improved properties of thedyes formed from them. The couplers described in the Vittum, Petersonand Porter applications are, in general, soluble in the developingsolution and not suitable for use in the emulsion layer because of theirtendency to diffuse from the layer. Thedyes formed from these couplers,however, have better light transmission characteristics and are morestable to heat and light than the dyes produced from previously knowncoupling components.

It is an object of the provide coupling components which have thedesirable properties of couplers containing the sulphonamide roup ichmay be incorporated present invention to in photographic emulsion layersas non-difiusing compounds. A further object is to provide novelphotographic couplers having desirable properties with respect to heatand light stability. A still further object is to provide photographiccouplers which form image dyes having desirable light transmissioncharacteristics. Other objects will appear from the followingdescription of my invention.

These 'objects are accomplished by replacing the free hydrogen atom ofthe sulphonamide group of couplers containing such group with radicalshaving the property of rendering the couplers non-diflfusing in gelatinor other colloidal media.

The color forming or coupler compounds which I have found to be suitablefor incorporation in silver halide emulsion layers according to myinvention are compounds having the following eneral structure:

Y 00- CH:-- CN where X is alkyl or phenyl substituted alkyl and Y is anyorganic substituent such as alkyl or aryl.

My invention may be illustrated by reference to the following CompoundsI and-II.

in Vittum, Peterson and Porter U. S. application Serial No. 266,152, nowPatent No. 2,271,238,

issued January-27, 1942. It is soluble in photographic developingsolutions. Compound II is identical with Compound I except that the freein the developer but may be incorporated in aphotographic emulsion layeras a. non-diflusing compound. My invention resides in the discoverythat, by the substitution of this free hydrogen I atom of thesulphonamide group with suitable organic radicals, the valuableproperties of the sulphonamide couplers may be retained, but thesolubility properties of the coupler are materially altered and thecoupler is rendered non-difiusing in gelatin or other colloidal media.

Compounds suitable for use as non-diflusing couplers according to myinvention are as follows:

-0 0-CHr-CN Z-cyanoacetylcoumarone-b-sulphon-di-mamylamlde l a-o o cnrcn2-cyanoacetylcoumerone-5 s1flphonN-ethyl--naphthalide -co-cm-cnN,N'-di-(Z-cyanoacetylooumarone-Hulphonyl): N,N-diphenylethylenediamlneQ-N-SOr- H H: Orr-sm- --cn NSO: CH -c o-cm-cn o2-cyanoacetylcoumarone-5-sulphon-N-methylanilide N-S O:- CH

l-c o-cm-crr 0 2-cyanoacetylcoumerone-5-mlphondimethylemlde2-cyanoacetylcoumarone-isulphon-(N ethylenilida)2-cyanoaoetylcoumarone-Hulphon-(N-n-propylanllide)Z-cyanoaoetylcoumarone-b-culpbon-(N-n-butylanlllde) oZ-cyanoacetylooumarone-b-eulphon-(N-n-amylanllide)2-cyanoaoetylooumnrone-5-sulphon-N(-n-amyD-pt-amylanlllde (IJsHn 12. N-S 0 C H Myanoecetylcoumarone-b-sulphon-(N-n-emyl-a-naphthelide) 13.CHzCHzCHz-N-OaS -CH lLoo-crn-cn 2-cyanoacet lcoumamne-fi-mlhon-N-(y-phenylpropyl)-p-(tert.-

y my? anilide l4. cmcmom-m-ms on ll-co-om-on o 1 (500.)manoacetylcoumarOMmflYhon-N-('rphenylpropyD-p-(90c.-

amy )-anillde l5.

CH -0 o-om-cn One of the substituents on the nitrogen atom or thesulphonamlde group, that is, Y in the general formula above, may be anyorganic substituent such as an alkyl or an aryl radical. The

other substituent bn the nitrogen atom, that is, X in the generalformula'above, is limited to alkyl, phenyl substituted alkyl or benzylradicals. This is the substituent which controls the solubility of thecoupler and produces the property 01 nondiffusability in gelatin. Thissubstituent may be a. simple methyl or ethyl radical or a phenylsubstituted alkyl radical such as benzyl or 'y-phenylpropyl. Theseradicals obviously may be considered henyl substituted alkyl radicals,benzyl being a phenyl substituted methyl radical. and 'yphenylpropylbeing a phenyl substituted propyl radical.

These couplers contain a methylene group which is reacted with theoxidation product of primary aromatic amino developing agents to producea dye image on photographic development. The CH2 group is presentbetween two negative centers in the group COCH2CN and is, therefore,reactive with the developing agent to produce a dye.

The aromatic amino developing agents used with the coupler compounds ofmy invention in clude the mono-, diand tri-aminoaryl compounds and theirderivatives formed by substitution in the amino group as well as in thering, such as alkylphenylenediamines and alkyl toluylenediamines. Thesecompounds are usually used in the salt form, such as the hydrochlorideor the sulphate, which are more stable than the amines themselves.Suitable compounds are diethyl-p-phenylenediamine hydrochloride,monomethyl p-phenylenediamineh'ydrochloride, di methylp-phenylenediaminehydrochloride and dimethyl-p-phenylenediaminesulphate. The pamino-phenols and their substitution products may also beused where the amino group is unsubstituted. All of these compounds havean unsubstituted amino group which enables the oxidation products of thedeveloper to couple with the color forming compounds to form a dyeimage.

The following examples are illustrative of developing solutions whichmay be used to develop emulsion. layers containing the couplers madeaccording to my invention.

The couplers'used according to my invention may be incorporated insilver halide emulsion layers in various ways but I prefer to form asolution of the sodium salt of the coupler in alcohol and add this tothe emulsion. For example, ,3 grams of coupler may be dissolved orsuspended in 50 cc. of ethyl alcohol and sodium hydroxide added in theamount'of 1 equivalent weights of the coupler. The sodium hydroxide maybe added as solid or as a concentrate solution. The sodium salt of thecoupler is thereby generated in a solution of 50 cc. of alcohol and thissolution is added to 1 liter of a gelatin silver halide emulsion. The pHof the emulsion may then be adjusted if desired by adding a suitableacid such as acetic or sulphuric acid to neutralize all or part of thesodium hydroxide used to form the sodium salt or the coupler.

The coupling components may be incorporated either in gelatin or inother colloidal materials such as collodion, organic esters of celluloseor synthetic resins. The emulsion may be carried by a transparent mediumsuch as glass, cellulose ester, or synthetic resin or a non-transparentreflecting medium such as paper or an opaque cellulose ester. Theemulsion may be coated as a single layer on the support or superposedlayers containing the couplers may be coated on one or both sides of thesupport. The superposed layers may be differentially sensitized for theformation of a natural color image in the well known manner.

The examples and compounds set forth in the present specification areillustrative only and it is to be understood that my invention is to betaken as limited only by the scope of the appended claims.

I claim:

1. A photographic emulsion for forming colored images comprising acolloidal carrier containing a sensitive silver halide and a couplercompound having the formula:

where X is selected from the class consisting of alkyl and phenylsubstituted alkyl radicals and Y is selected from the class consistingof alkyl -and aryl radicals.

2. A photographic emulsion for forming colored images comprising acolloidal carrier containing a sensitive silver halide and a couplercompound having the formula:

N-so

where X and Y are alkyl radicals.

3. A photographic emulsion for forming colored images comprising acolloidal carrier containing a sensitive silver halide and a couplercompound having the formula:

o where X is a phenyl substituted alkyl radical and Y is an arylradical.

5. In the method of producing a colored photographic image in a gelatinosilver halide emulsion layer, the step which comprises treating theexing the formula:

where X is selected from the class consisting of alkyl and phenylsubstituted alkyl radicals and Y is selected from the class consistingof alkyl 'where X and Y are alkyl radicals, with a developer containinga primary aromatic amino developing agent.

7. In the method of producing a colored photographic image in a gelatinosilver halide emulposed layer containing a coupler compound havsionlayer, the step which comprises treating the exposed layer containing acoupler compound having the formula:

\'-N-SO \"J-O 043111-051 I where X is an alkyl radical and Y is an arylradical, with a developer containing a primary aromatic amino developingagent.

3. In the method of producing a colored photographic image in a gelatinosilver halide emulsion layer, the step which comprises treating theexposed layer containing a coupler compound having the formula:

0/ O Hz-CN where X is a phenyl substituted alkyl radical and Y is anaryl radical, with a developer containing a primary aromatic aminodeveloping agent.

ARNOLD WEISSBERGER.

CERTIFICATE OF CORRECTION. Patent No.2,558,6'(7. January 1;, 191414.-

ARNOLD WEISSBERGER.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,866- ond column, lines 62 and 68, Formulas i5 and 16 respectively, forthat portion reading CH -CH" read --CH -CN-- and that the said LettersPatent should be read with this correction therein that the same mayform to the record of the case in the Patent Office.

Signed and. sealed this 5rd day of October, A. D. 19 4 1 Leslie Frazer 8Acting Commissioner of Patents.

